Removal of high-dose ion-implanted photoresist using self-assembled monolayers in solvent systems

ABSTRACT

A method and self assembled monolayer (SAM)-containing compositions for removing bulk and hardened photoresist material from microelectronic devices have been developed. The SAM-containing composition includes at least one solvent, at least one catalyst, at least one SAM component, and optionally a surfactant. The SAM-containing compositions effectively remove the hardened photoresist material while simultaneously passivating the underlying silicon-containing layer(s) in a one step process.

FIELD OF THE INVENTION

The present invention relates to self-assembled monolayer(SAM)-containing compositions useful for the removal of bulk andhardened photoresist from the surface of microelectronic devices, andmethods of using said compositions for removal of same.

DESCRIPTION OF THE RELATED ART

As semiconductor devices have become more integrated and miniaturized,ion implantation has been extensively employed during front-end-of-line(FEOL) processing to accurately control impurity distributions in themicroelectronic device and to add dopant atoms, e.g., As, B and P, tothe exposed device layers. The concentration and depth of the dopantimpurity is controlled by varying the dose of the dopant, theacceleration energy, and the ion current. Prior to subsequentprocessing, the ion-implanted photoresist layer must be removed. Variousprocesses have been used in the past for the removal of said hardenedphotoresist including, but not limited to, wet chemical etchingprocesses, e.g., in a mixed solution of sulphuric acid and hydrogenperoxide, and dry plasma etching processes, e.g., in an oxygen plasmaashing process.

Unfortunately, when high doses of ions (e.g., doses greater than about1×10¹⁵ atoms cm⁻²), at low (5 keV), medium (10 keV) and high (20 keV)implant energy, are implanted in the desired layer, they are alsoimplanted throughout the photoresist layer, particularly the exposedsurface of the photoresist, which becomes physically and chemicallyrigid. The rigid ion-implanted photoresist layer, also referred to asthe carbonized region or “crust,” has proven difficult to remove.

Presently, the removal of the ion-implanted photoresist and othercontaminants is usually performed by a plasma etch method followed by amulti-step wet strip process, typically using aqueous-based etchantformulations to remove photoresist, post-etch residue and othercontaminants. Wet strip treatments in the art generally involve the useof strong acids, bases, solvents, and oxidizing agents.Disadvantageously, however, wet strip treatments also etch theunderlying silicon-containing layers, such as the substrate and gateoxide, and/or increase the gate oxide thickness.

As the feature sizes continue to decrease, satisfying the aforementionedremoval requirements becomes significantly more challenging using theaqueous-based etchant formulations of the prior art. Water has a highsurface tension which limits or prevents access to the smaller imagenodes with high aspect ratios, and therefore, removing the residues inthe crevices or grooves becomes more difficult. In addition,aqueous-based etchant formulations often leave previously dissolvedsolutes behind in the trenches or vias upon evaporative drying, whichinhibit conduction and reduce device yield. Furthermore, underlyingporous low-k dielectric materials do not have sufficient mechanicalstrength to withstand the capillary stress of high surface tensionliquids such as water, resulting in pattern collapse of the structures.Aqueous etchant formulations can also strongly alter important materialproperties of the low-k materials, including dielectric constant,mechanical strength, moisture uptake, coefficient of thermal expansion,and adhesion to different substrates.

Therefore, it would be a significant advance in the art to provide animproved composition that overcomes the deficiencies of the prior artrelating to the removal of bulk and hardened photoresist frommicroelectronic devices. The improved composition shall effectivelyremove bulk and hardened photoresist in a one-step or multi-stepprocess, without the need for a plasma etch step and withoutsubstantially over-etching the underlying silicon-containing layer(s).

SUMMARY OF THE INVENTION

The present invention relates to self-assembled monolayer(SAM)-containing compositions useful for the removal of bulk andhardened photoresist from the surface of microelectronic devices,methods of making and methods of using said compositions for removal ofsame, and improved microelectronic devices made using the same.

In one aspect, the invention relates to a self assembled monolayer(SAM)-containing composition, comprising at least one solvent, at leastone catalyst, at least one SAM component, and optionally at least onesurfactant, wherein said SAM-containing composition is suitable forremoving bulk and hardened photoresist material from a microelectronicdevice having said photoresist material thereon.

In another aspect, the present invention relates to a kit comprising, inone or more containers, SAM-containing composition reagents, wherein theSAM-containing composition comprises at least one solvent, at least onecatalyst, at least one SAM component, and optionally at least onesurfactant, and wherein the kit is adapted to form a SAM-containingcomposition suitable for removing bulk and hardened photoresist materialfrom a microelectronic device having said photoresist material thereon.

In a further aspect, the present invention relates to a method ofremoving bulk and hardened photoresist material from a microelectronicdevice having said photoresist material thereon, said method comprisingcontacting the microelectronic device with a SAM-containing compositionfor sufficient time and under sufficient contacting conditions to atleast partially remove said photoresist material from themicroelectronic device, wherein the SAM-containing composition includesat least one solvent, at least one catalyst, at least one SAM component,and optionally at least one surfactant.

In a still further aspect, the present invention relates to a method ofremoving bulk and hardened photoresist material from a microelectronicdevice having said photoresist material thereon, said method comprisingcontacting the microelectronic device with a SAM-containing compositionfor sufficient time to at least partially passivate a silicon-containinglayer underlying the photoresist material, and contacting themicroelectronic device with an etchant-containing removal composition toat least partially remove said photoresist material from themicroelectronic device, wherein the SAM-containing composition comprisesa non-halide containing SAM component.

In another aspect, the present invention relates to a method of removingbulk and hardened photoresist material from a microelectronic devicehaving said photoresist material thereon, said method comprisingcontacting the microelectronic device with a SAM-containing compositionfor sufficient time to at least partially remove said photoresistmaterial from the microelectronic device, wherein the SAM-containingcomposition is devoid of an etchant component.

In yet another aspect, the present invention relates to a method ofmanufacturing a microelectronic device, said method comprisingcontacting the microelectronic device with an SAM-containing compositionfor sufficient time to at least partially remove bulk and hardenedphotoresist material from the microelectronic device having saidphotoresist material thereon, wherein the SAM-containing compositionincludes at least one solvent, at least one catalyst, at least one SAMcomponent, and optionally at least one surfactant, and optionallyincorporating said cleaned microelectronic device into a product.

Other aspects, features and embodiments of the invention will be morefully apparent from the ensuing disclosure and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1D are atomic force micrographs of the microelectronic devicesurfaces at contacting times=1 min, 30 min, 1 hour and 15 hours,respectively, following contact of a SAM-containing compositionincluding 1 mmol Cl₃SiMe and 2 mmol Et₃N in 10 mL of toluene, with thedevice surface at a contacting temperature of 70° C.

FIG. 2 illustrates the cleaning efficiency of a SAM-containingcomposition of the present invention as a function of temperature forfour different microelectronic device layers including a bulk blanketedphotoresist layer (Bulk PR), a blanketed ion-implanted photoresist layer(Crust), a bulk patterned photoresist layer (Patterned PR) and apatterned ion-implanted photoresist layer (Patterned Crust).

FIGS. 3A-3C are atomic force micrographs of the microelectronic devicesurfaces following contact of a SAM-containing composition includingClSiMe₃ (FIG. 3A), Cl₂SiMe₂ (FIG. 3B), and Cl₃SiMe (FIG. 3C), in 2 mmolEt₃N in 10 mL of toluene, with the device surface at a contactingtemperature of 70° C. for 30 min.

FIGS. 4A-4C are optical microscope images (FIG. 4A) and scanningelectron microscopic (SEM) images (FIGS. 4B-4C) of densely patterned,ion implanted photoresist on a microelectronic device surface.

FIGS. 5A-5C are optical microscope images of the microelectronic devicesurfaces following contact of a SAM-containing composition includingClSiMe₃ (FIG. 5A), Cl₂SiMe₂ (FIG. 5B), and Cl₃SiMe (FIG. 5C), at 70° C.for 30 min.

FIG. 6 illustrates the removal efficiency of a SAM-containingcomposition of the present invention as a function of SAM functionalityfor the four different microelectronic device layers including a bulkblanketed photoresist layer (Bulk PR), a blanketed ion-implantedphotoresist layer (Crust), a bulk patterned photoresist layer (PatternedPR) and a patterned ion-implanted photoresist layer (Patterned Crust).

FIGS. 7A-7C are optical microscope images of the control surface (FIG.7A), the surface following cleaning and passivation using aSAM-containing composition of the invention (FIG. 7B), and the surfacefollowing depassivation according to the invention (FIG. 7C).

FIGS. 8A-8E are scanning electron micrographs of the control surface(FIG. 8A), the surface following cleaning and passivation using aSAM-containing composition of the invention (FIG. 8B), the surfacefollowing depassivation at a 90° angle view (FIG. 8C) and a 60° angleview (FIG. 8D), and a purposely over-etched surface followingdepassivation (FIG. 8E).

DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS THEREOF

The present invention is based on the discovery of self-assembledmonolayer (SAM)-containing compositions that are highly efficacious forthe removal of bulk and hardened photoresist from the surface ofmicroelectronic devices, while maintaining the integrity of theunderlying silicon-containing layer(s).

“Bulk photoresist,” as used herein, corresponds to the non-carbonizedphotoresist on the microelectronic device surface, specifically adjacentand below the hardened photoresist crust.

“Hardened photoresist” as used herein includes, but is not limited to,photoresist that has been plasma etched, e.g., during back-end-of-line(BEOL) dual-damascene processing of integrated circuits, ion implanted,e.g., during front-end-of-line (FEOL) processing to implant dopantspecies in the appropriate layers of the semiconductor wafer, and/or anyother methodology whereby a carbonized or highly cross-linked crustforms on the exposed surface of the bulk photoresist.

As used herein, “underlying silicon-containing” layer corresponds to thelayer(s) immediately below the bulk and/or the hardened photoresistincluding: silicon; silicon oxide, including gate oxides (e.g.,thermally or chemically grown SiO₂) and TEOS; silicon nitride; and low-ksilicon-containing materials. As defined herein, “low-ksilicon-containing material” corresponds to any material used as adielectric material in a layered microelectronic device, wherein thematerial has a dielectric constant less than about 3.5. Preferably, thelow-k dielectric materials include low-polarity materials such assilicon-containing organic polymers, silicon-containing hybridorganic/inorganic materials, organosilicate glass (OSG), TEOS,fluorinated silicate glass (FSG), silicon dioxide, and carbon-dopedoxide (CDO) glass. It is to be appreciated that the low-k dielectricmaterials may have varying densities and varying porosities.

“Microelectronic device” corresponds to semiconductor substrates, flatpanel displays, and microelectromechanical systems (MEMS), manufacturedfor use in microelectronic, integrated circuit, or computer chipapplications. It is to be understood that the term “microelectronicdevice” is not meant to be limiting in any way and includes anysubstrate that will eventually become a microelectronic device ormicroelectronic assembly.

As defined herein, “substantially over-etching” corresponds to greaterthan about 10% removal, more preferably greater than about 5% removal,and most preferably greater than about 2% removal, of the adjacentunderlying silicon-containing layer(s) following contact, according tothe process of the present invention, of the SAM-containing compositionsof the invention with the microelectronic device having said underlyinglayer(s). In other words, most preferably no more than 2% of theunderlying silicon-containing layer(s) are etched using the compositionsof the present invention for the prescribed times.

As used herein, “about” is intended to correspond to ±5% of the statedvalue.

As used herein, “suitability” for removing bulk and hardened photoresistmaterial from a microelectronic device having said photoresist materialthereon, corresponds to at least partial removal of said photoresistmaterial from the microelectronic device. Preferably, at least 90% ofthe photoresist material is removed from the microelectronic deviceusing the compositions of the invention, more preferably, at least 95%,and most preferably at least 99% of the photoresist material, isremoved.

“Dense fluid,” as used herein, corresponds to a supercritical fluid or asubcritical fluid. The term “supercritical fluid” is used herein todenote a material which is under conditions of not lower than a criticaltemperature, T_(c), and not less than a critical pressure, P_(c), in apressure-temperature diagram of an intended compound. The preferredsupercritical fluid employed in the present invention is CO₂, which maybe used alone or in an admixture with another additive such as Ar, NH₃,N₂, CH₄, C₂H₄, CHF₃, C₂H₆, n-C₃H₈, H₂O, N₂O and the like. The term“subcritical fluid” describes a solvent in the subcritical state, i.e.,below the critical temperature and/or below the critical pressureassociated with that particular solvent. Preferably, the subcriticalfluid is a high pressure liquid of varying density.

Importantly, the SAM-containing compositions of the present inventionmust possess good metal-containing material compatibility, e.g., a lowetch rate on the metal-containing material. Metal-containing materialsof interest include, but are not limited to, copper, tungsten, cobalt,aluminum, tantalum, titanium and ruthenium and silicides and nitridesthereof.

Self assembled monolayers (SAMs) are known to passivate varioussurfaces, including, but not limited to, metals (e.g., copper, gold,etc), and oxides of titanium, hafnium, silicon, and aluminum. SAMsinclude silanes having at least one leaving group, e.g., a halide, saidsilane readily forming a covalent bond at an oxygen group on asilicon-containing surface (i.e., via a silylation reaction). Thesilanes themselves may further include covalently bonded inertmolecules, such as polyethylene glycol (PEG), whereby followingattachment with the silicon-containing surface, the PEG-silane can blockother molecules from binding with said surface. PEG-silane SAMs arepopular because they are thin (i.e., non-bulky) and hydrophilic, andlinkage of the PEG molecule with the silicon-containing surface resultsin a non-sticky, water-like layer. In contrast, alkylchlorosilanes maybe used to form a hydrophobic surface, if necessary.

Compositions of the invention may be embodied in a wide variety ofspecific formulations, as hereinafter more fully described.

In all such compositions, wherein specific components of the compositionare discussed in reference to weight percentage ranges including a zerolower limit, it will be understood that such components may be presentor absent in various specific embodiments of the composition, and thatin instances where such components are present, they may be present atconcentrations as low as 0.01 weight percent, based on the total weightof the composition in which such components are employed.

In one aspect, the invention relates to a liquid SAM-containingcomposition useful in removing bulk and hardened photoresist from amicroelectronic device. The liquid composition according to oneembodiment comprises at least one SAM component, optionally at least onesolvent, optionally at least one catalyst, and optionally at least onesurfactant. The liquid composition according to another embodimentcomprises at least one SAM component, at least one catalyst, optionallyat least one solvent, and optionally at least one surfactant. The liquidcomposition according to yet another embodiment comprises at least oneSAM component, at least one solvent, at least one catalyst, andoptionally at least one surfactant. Importantly, depending on the natureof the solvent chosen, the solvent may act concurrently as the catalyst.

In one embodiment, the invention relates to a liquid SAM-containingcomposition useful in removing bulk and hardened photoresist from amicroelectronic device, wherein the catalyst concurrently acts as thesolvent. The liquid composition according to this embodiment comprisesat least one catalyst, at least one SAM component, and optionally atleast one surfactant present in the following ranges, based on the totalweight of the composition: component of % by weight catalyst(s) about85.0% to about 99.99% SAM(s) about 0.01% to about 10.0% Surfactant(s) 0%to about 10.0%

In a particularly preferred embodiment, the invention relates to aliquid SAM-containing composition useful in removing bulk and hardenedphotoresist from a microelectronic device. The liquid compositionaccording to this embodiment comprises at least one solvent, at leastone catalyst, at least one SAM component, and optionally at least onesurfactant present in the following ranges, based on the total weight ofthe composition: component of % by weight solvent(s) about 75.0% toabout 99.98% SAM(s) about 0.01% to about 10.0% catalyst(s) about 0.01%to about 10.0% Surfactant(s) 0% to about 10.0%

In one aspect, the range of mole ratios of SAM(s) relative tocatalyst(s) in the liquid SAM-containing composition is about 1:10 toabout 5:1, more preferably about 1:5 to about 1:1; the range of moleratios of SAM(s) relative to liquid solvent(s) is about 1:200 to about1:50, more preferably about 1:125 to about 1:75; and the range of moleratios of SAM(s) relative to surfactant(s) (when present) is about 1:10to about 5:1.

In the broad practice of the invention, the liquid SAM-containingcomposition may comprise, consist of, or consist essentially of at leastone solvent, at least one catalyst, at least one SAM component, andoptionally at least one surfactant. In general, the specific proportionsand amounts of solvent(s), catalyst(s), SAM component(s), and optionalsurfactant(s), in relation to each other, may be suitably varied toprovide the desired removal action of the liquid SAM-containingcomposition for the bulk and hardened photoresist and/or processingequipment, as readily determinable within the skill of the art withoutundue effort.

Solvent species useful in the compositions of the invention may benon-polar or polar in nature. Illustrative non-polar species include,but are not limited to, toluene, decane, dodecane, octane, pentane,hexane, tetrahydrofuran (THF) and carbon dioxide (subcritical orsupercritical). Illustrative polar species include methanol, ethanol,isopropanol, N-methylpyrrolidinone, N-octylpyrrolidinone,N-phenylpyrrolidinone, dimethylsulfoxide (DMSO), sulfolane, ethyllactate, ethyl acetate, toluene, acetone, methyl carbitol, butylcarbitol, hexyl carbitol, monoethanolamine, butyrol lactone, diglycolamine, alkyl ammonium fluoride, γ-butyrolactone, butylene carbonate,ethylene carbonate, and propylene carbonate and mixtures thereof.Preferably, the solvent comprises a non-polar species. Toluene isespecially preferred.

The SAM component may include alkoxyhalosilanes including (RO)₃SiX,(RO)₂SiX₂, (RO)SiX₃, where X may be the same as or different from oneanother and is selected from the group consisting of F, Cl, Br or I, andRO may be the same as or different from one another and is selected fromthe group consisting of straight-chained or branched C₁-C₂₀ alkoxyspecies such as methoxy, ethoxy, propoxy, etc., or combinations thereof.Preferably, the SAM component includes alkylhalosilanes of the nature(R)₃SiX, (R)₂SiX₂, (R)SiX₃, where X may be the same as or different fromone another and is selected from the group consisting of F, Cl, Br or I,and R may be the same as or different from one another and is selectedfrom the group consisting of straight-chained, branched or cyclic C₁-C₂₀alkyl species such as methyl, ethyl, propyl, butyl, octyl, decyl,dodecyl, etc., or combinations thereof. Fluorinated alkyl and alkoxyderivatives may also be used. Preferably, the SAM component includesalkylhalosilanes where X=Cl and R=methyl. In another alternative, theSAM component has a PEG molecule attached thereto.

Although not wishing to be bound by theory, the catalyst is included inthe composition of the invention to initiate the silylation reaction andspeed up the passivation of the underlying silicon-containing layer(s).Preferably, the catalysts include amines such as trimethylamine,triethylamine, butylamine, pyridine, and any other nucleophilic compoundthat aids in the removal of a halogen leaving group from the SAMcomponent. It is thought that the amine catalyst promotes an in situsilylation reaction, whereby the SAM silane covalently attaches tooxygen atoms on the underlying silicon-containing layer(s), with thesimultaneous generation of a protonated leaving group, e.g., HX.Accordingly, the underlying silicon-containing layer is passivated bythe covalently bound silane, while the generated protonated leavinggroup is available for removal of the hardened photoresist material.Importantly, depending on the nature of the solvent chosen, the solventmay act concurrently as the catalyst.

The liquid SAM-containing compositions of the invention may furtherinclude a surfactant to assist in the removal of the resist from thesurface of the microelectronic device. Illustrative surfactants include,but are not limited to, fluoroalkyl surfactants, polyethylene glycols,polypropylene glycols, polyethylene or polypropylene glycol ethers,carboxylic acid salts, dodecylbenzenesulfonic acid or salts thereof,polyacrylate polymers, dinonylphenyl polyoxyethylene, silicone ormodified silicone polymers, acetylenic diols or modified acetylenicdiols, alkylammonium or modified alkylammonium salts, as well ascombinations of the foregoing surfactants.

In a preferred embodiment, the liquid SAM-containing compositionincludes less than about 1 wt. % water, more preferably less than about0.5 wt. % water, and most preferably less than about 0.25 wt. % water,based on the total weight of the composition. Further, preferably the atleast one SAM component does not undergo substantial polymerization atthe microelectronic device surface. For example, preferably less than 5wt. % of the SAM component polymerizes at the microelectronic devicesurface, more preferably less than 2 wt. %, even more preferably lessthan 1 wt. %, and most preferably less than 0.1 wt. % of the SAMcomponent polymerizes at the microelectronic device surface.

In general, the specific proportions and amounts of at least onesolvent, at least one catalyst, at least one SAM component, andoptionally at least one surfactant, in relation to each other, may besuitably varied to provide the desired cleaning and passivating actionof the liquid SAM-containing composition for the bulk and hardenedphotoresist to be removed from the microelectronic device. Such specificproportions and amounts are readily determinable by simple experimentwithin the skill of the art without undue effort. Most preferably, theSAM-containing component(s) and the catalyst(s) are present in an amounteffective to remove bulk and hardened photoresist material from amicroelectronic device having said material thereon.

It is to be understood that the phrase “removing bulk and hardenedphotoresist material from a microelectronic device” is not meant to belimiting in any way and includes the removal of bulk and hardenedphotoresist material from any substrate that will eventually become amicroelectronic device.

It is also contemplated herein that the liquid SAM-containingcomposition of the present invention may be used to remove hardenedphotoresist, e.g., BEOL hardened photoresist, bottom anti-reflectivecoating (BARC) material, post-CMP residue, BARC residue and/orpost-ash/post-etch photoresist, while simultaneously passivating theunderlying silicon-containing layer(s) or any other hydrophilic surfacehaving hydroxyl-terminated groups in need of passivation. In addition,the liquid SAM-containing compositions of the present invention may beused to remove contaminating materials from photomask materials forre-use thereof.

The liquid SAM-containing compositions of the invention may optionallybe formulated with additional components to further enhance thepassivation and removal capability of the composition, or to otherwiseimprove the character of the composition, i.e., provide metalpassivation. Accordingly, the composition may be formulated withstabilizers, complexing agents, passivators, e.g., Cu passivatingagents, and/or corrosion inhibitors.

The liquid SAM-containing compositions of the invention are easilyformulated by the mixture of solvent(s), catalyst(s), SAM component(s),and optional surfactant(s) with gentle agitation. The solvent(s),catalyst(s), SAM component(s), and optional surfactant(s) may be readilyformulated as single-package formulations or multi-part formulationsthat are mixed at the point of use. The individual parts of themulti-part formulation may be mixed at the tool or in a storage tankupstream of the tool. The concentrations of the single-packageformulation or the individual parts of the multi-part formulations maybe widely varied in specific multiples, i.e., more dilute or moreconcentrated, in the broad practice of the invention, and it will beappreciated that the liquid SAM-containing compositions of the inventioncan variously and alternatively comprise, consist or consist essentiallyof any combination of ingredients consistent with the disclosure herein.

Accordingly, another aspect of the invention relates to a kit including,in one or more containers, one or more components adapted to form thecompositions of the invention. Preferably, the kit includes, in one ormore containers, at least one solvent, at least one SAM component, andoptionally at least one surfactant for combining with the at least onecatalyst at the fab. According to another embodiment, the kit includes,in one or more containers, at least one SAM component, and optionally atleast one surfactant for combining with the at least one solvent and theat least one catalyst at the fab. In yet another embodiment, the kitincludes in one container at least one SAM component in solvent and inanother container at least one catalyst in solvent for combining at thefab. For example, the containers of the kit may be NOWPak® containers(Advanced Technology Materials, Inc., Danbury, Conn., USA).

In yet another embodiment, the invention relates to a liquidSAM-containing composition useful in removing bulk and hardenedphotoresist from a microelectronic device, wherein the liquidSAM-containing composition includes at least one solvent, at least onecatalyst, at least one SAM component, optionally at least onesurfactant, and photoresist residue material, wherein the photoresist isbulk and/or hardened photoresist. Importantly, the residue material maybe dissolved and/or suspended in the liquid SAM-containing compositionof the invention. In still another embodiment, the photoresist residuematerial includes an ion selected from the group consisting of boronions, arsenic ions, phosphorus ions, indium ions, and antimony ions.

In yet another aspect, the invention relates to dense SAM-containingcompositions including dense fluids, e.g., supercritical fluids (SCF),as the primary solvent system. Because of its readily manufacturedcharacter and its lack of toxicity and negligible environmental effects,supercritical carbon dioxide (SCCO₂) is the preferred SCF. SCCO₂ is anattractive reagent for removal of microelectronic device processcontaminants, since SCCO₂ has the characteristics of both a liquid and agas. Like a gas, it diffuses rapidly, has low viscosity, near-zerosurface tension, and penetrates easily into deep trenches and vias. Likea liquid, it has bulk flow capability as a “wash” medium. SCCO₂ has adensity comparable to organic solvents and also has the advantage ofbeing recyclable, thus minimizing waste storage and disposalrequirements.

The dense SAM-containing composition according to one embodimentcomprises SCCO₂ and the liquid SAM-containing composition, i.e., aSAM-containing concentrate, in the following ranges, based on the totalweight of the composition: component of % by weight SCCO₂ about 95.0% toabout 99.99% liquid SAM-containing composition about 0.01% to about10.0%where the liquid SAM-containing composition comprises about 75.0% toabout 90.0% co-solvent, about 0.01% to about 10.0% SAM component, about0.01% to about 10.0% catalyst and optionally 0 to about 10.0%surfactant, wherein the co-solvent(s), SAM-component(s), catalyst(s) andoptional surfactant(s) contemplated include the aforementioned species.

In one aspect, the range of mole ratios of liquid SAM-containingcomposition relative to SCCO₂ in the dense SAM-containing composition isabout 1:200 to about 1:4, more preferably about 1:100 to about 1:6.

In the broad practice of the invention, the dense SAM-containingcomposition may comprise, consist of, or consist essentially of SCCO₂and the liquid SAM-containing composition, i.e., at least one additionalsolvent, at least one catalyst, at least one SAM component, andoptionally at least one surfactant. In general, the specific proportionsand amounts of SCCO₂ and liquid SAM-containing composition, in relationto each other, may be suitably varied to provide the desired removalaction of the dense SAM-containing composition for the bulk and hardenedphotoresist and/or processing equipment, as readily determinable withinthe skill of the art without undue effort. Importantly, the liquidSAM-containing composition may be at least partially dissolved and/orsuspended within the dense fluid of the dense SAM-containingcomposition.

In yet another embodiment, the invention relates to a denseSAM-containing composition useful in removing bulk and hardenedphotoresist from a microelectronic device, wherein the denseSAM-containing composition includes SCCO₂, at least one solvent, atleast one catalyst, at least one SAM component, optionally at least onesurfactant, and photoresist residue material, wherein the photoresist isbulk and/or hardened photoresist. Importantly, the residue material maybe dissolved and/or suspended in the dense SAM-containing composition ofthe invention. In still another embodiment, the photoresist residuematerial includes an ion selected from the group consisting of boronions, arsenic ions, phosphorus ions, indium ions, and antimony ions.

It is also contemplated herein that the dense SAM-containing compositionof the present invention may be used to remove hardened photoresist,e.g., BEOL hardened photoresist, bottom anti-reflective coating (BARC)material, post-CMP residue, BARC residue and/or post-ash/post-etchphotoresist, while simultaneously passivating the underlyingsilicon-containing layer(s) or any other hydrophilic surface havinghydroxyl-terminated groups in need of passivation. In addition, thedense SAM-containing compositions of the present invention may be usedto remove contaminating materials from photomask materials for re-usethereof.

In yet another aspect, the invention relates to methods of removal ofbulk and hardened photoresist from a microelectronic device using theSAM-containing compositions described herein. For example, trench andvia structures on the patterned devices may be cleaned while maintainingthe structural integrity of the underlying silicon-containing layersusing SAM passivation. It should be appreciated by one skilled in theart that the SAM-containing compositions may be used in a one-step ormulti-step removal process.

The SAM-containing compositions of the present invention overcome thedisadvantages of the prior art removal techniques by reversiblypassivating the underlying silicon-containing layer(s), whilesimultaneously removing the bulk and hardened photoresist depositedthereon.

The liquid SAM-containing compositions of the present invention arereadily formulated by simple mixing of ingredients, e.g., in a mixingvessel or the cleaning vessel under gentle agitation. The denseSAM-containing compositions are readily formulated by static or dynamicmixing at the appropriate temperature and pressure.

In passivation and removal application, the liquid SAM-containingcomposition is applied in any suitable manner to the microelectronicdevice having photoresist material thereon, e.g., by spraying thecomposition on the surface of the device, by dipping (in a volume of thecomposition) of the device including the photoresist material, bycontacting the device with another material, e.g., a pad, or fibroussorbent applicator element, that is saturated with the composition, bycontacting the device including the photoresist material with acirculating composition, or by any other suitable means, manner ortechnique, by which the liquid SAM-containing composition is broughtinto contact with the photoresist material on the microelectronicdevice. The passivation and removal application may be static ordynamic, as readily determined by one skilled in the art.

In use of the compositions of the invention for removing photoresistmaterial from microelectronic device surfaces having same thereon, theliquid SAM-containing composition typically is contacted with the devicesurface for a time of from about 1 to about 60 minutes, the preferredtime being dependent on the dopant ion dose and the implant energyemployed during ion implantation, wherein the higher the dopant ion doseand/or implant energy, the longer the contacting time required.Preferably, temperature is in a range of from about 20° C. to about 80°C., preferably about 30° C. to about 80° C., most preferably about 70°C. Such contacting times and temperatures are illustrative, and anyother suitable time and temperature conditions may be employed that areefficacious to at least partially remove the photoresist material fromthe device surface, within the broad practice of the invention. Asdefined herein, “at least partial removal” corresponds to at least 90%removal of bulk and hardened photoresist, preferably at least 95%removal. Most preferably, at least 99% of said bulk and hardenedphotoresist material is removed using the compositions of the presentinvention.

Following the achievement of the desired passivation and cleaningaction, the microelectronic device may be thoroughly rinsed with copiousamounts of ethanol and/or THF to remove any residual chemical additives.

The SAM-containing compositions of the invention selectively remove 100%of highly doped (with 2×10¹⁵ As ions cm⁻²) photoresist (500-700 nmthick) having a hardened, cross-linked carbonized crust ranging from30-70 nm in thickness. Importantly, the hardened crust is removedwithout substantially over-etching the underlying silicon-containinglayer(s).

For passivation and cleaning applications using the dense SAM-containingcompositions, the microelectronic device surface having the photoresistthereon is contacted with the dense SAM-containing composition, atsuitable elevated pressures, e.g., in a pressurized contacting chamberto which the dense SAM-containing composition is supplied at suitablevolumetric rate and amount to effect the desired contacting operation,for at least partial removal of the photoresist from the microelectronicdevice surface. The chamber may be a batch or single wafer chamber, forcontinuous, pulsed or static cleaning. The passivation and removal ofthe hardened photoresist by the dense SAM-containing composition may beenhanced by use of elevated temperature and/or pressure conditionsduring contacting of the photoresist with the dense SAM-containingcomposition.

The appropriate dense SAM-containing composition may be employed tocontact a microelectronic device surface having photoresist thereon at apressure in a range of from about 1,500 to about 4,500 psi forsufficient time to effect the desired removal of the photoresist, e.g.,for a contacting time in a range of from about 5 minutes to about 30minutes and a temperature of from about 40° C. to about 75° C., althoughgreater or lesser contacting durations and temperatures may beadvantageously employed in the broad practice of the present invention.

The removal process using the dense SAM-containing composition mayinclude a static soak, a dynamic cleaning mode, or sequential processingsteps including dynamic flow of the dense SAM-containing compositionover the microelectronic device surface, followed by a static soak ofthe device in the dense SAM-containing composition, with the respectivedynamic flow and static soak steps being carried out alternatingly andrepetitively, in a cycle of such alternating steps.

A “dynamic” contacting mode involves continuous flow of the compositionover the device surface, to maximize the mass transfer gradient andeffect complete removal of the resist from the surface. A “static soak”contacting mode involves contacting the device surface with a staticvolume of the composition, and maintaining contact therewith for acontinued (soaking) period of time.

Following the contacting of the dense SAM-containing composition to themicroelectronic device surface, the device thereafter preferably iswashed with rinsing solution, for example, aliquots of SCF/co-solventsolution, e.g., SCCO₂/methanol (80%/20%) solution, and pure SCF, toremove any residual precipitated chemical additives from the region ofthe device surface in which resist removal has been effected.

It will be appreciated that specific contacting conditions for theliquid SAM-containing and the dense SAM-containing compositions of theinvention are readily determinable within the skill of the art, based onthe disclosure herein, and that the specific proportions of ingredientsand concentrations of ingredients in the compositions of the inventionmay be widely varied while achieving desired passivation of theunderlying silicon-containing layer(s) and removal of the hardenedphotoresist material on the microelectronic device surface.

Another aspect of the invention relates to methods of removal of bulkand hardened photoresist from a microelectronic device, said methodincluding passivation of the underlying silicon-containing layer(s) onthe microelectronic device surface using non-halide containing SAMcomponent, e.g., hexamethyldisilazane (HMDS), and removing the bulk andhardened photoresist from the microelectronic device using anetchant-containing removal composition. Suitable etchant-containingremoval compositions include without limitation, hydrogen fluoride (HF),ammonium fluoride (NH₄F), alkyl hydrogen fluoride (NRH₃F),dialkylammonium hydrogen fluoride (NR₂H₂F), trialkylammonium hydrogenfluoride (NR₃HF), trialkylammonium trihydrogen fluoride (NR₃(3 HF)),tetraallcylammonium fluoride (NR₄F), pyridine-HF complex, pyridine/HClcomplex, pyridine/HBr complex, triethylamine/HF complex,triethylamine/HCl complex, monoethanolamine/HF complex,triethanolamine/HF complex, triethylamine/formic acid complex, and xenondifluoride (XeF₂), wherein each R in the aforementioned R-substitutedspecies is independently selected from C₁-C₈ alkyl and C₆-C₁₀ aryl.Additional species are disclosed in co-pending U.S. Provisional PatentApplication No. 60/672,157, filed Apr. 15, 2005 in the name of Pamela M.Visintin et al. for “Dense Fluid Formulations for Cleaning Ion-ImplantedPhotoresist Layers from Microelectronic Devices,” which is incorporatedherein by reference in its entirety.

In yet another aspect, the invention relates to a method of removingbulk and hardened photoresist material from a microelectronic devicehaving said photoresist material thereon, said method comprisingcontacting the microelectronic device with a SAM-containing compositionfor sufficient time to at least partially remove said photoresistmaterial from the microelectronic device, with the provision that theSAM-containing composition is devoid of an etchant component selectedfrom the group consisting of hydrogen fluoride, ammonium fluoride,ammonium bifluorides and other well-known fluoride etchant species.

Regardless of the method used to remove the hardened photoresist fromthe microelectronic device, a further aspect of the invention includesthe removal of the SAM passivating layer from the surface of themicroelectronic device subsequent to the removal of the photoresistmaterial therefrom, referred to herein as “depassivation.”

When carbon contamination due to the passivating alkyl groups on thewafer surface is unacceptable (approximately 3 to 10 Å monolayer ofmethyl groups when Cl₃SiMe is the SAM used), the SAM may be removedusing strong acids such as H₂SO₄, however, this may cause unwantedoxidation of the underlying silicon-containing layer(s). Thus, diluteinorganic acids including halide ions, such as HCl and HF, are preferredunder optimized process conditions. The halide ions will readily attacka passivating Si—O—Si bond at the SAM-device surface interface and thus“depassivate” the device surface. However, special care should be takento minimize over-etching of the silicon-containing layer(s) on thedevice surface.

The inventors have previously shown that anhydrous solutions ofHF/Pyridine (1:1 mole ratio) in DMSO are known to etch thermal oxide,TEOS, silicon nitride, and polysilicon at rates less than <0.1 Å min⁻¹.Thus, the depassivating solution may include about 0.01 wt % to about 2wt. % dilute inorganic acid/amine complex and/or inorganic acid in asolvent to depassivate the device surface with only slight fluorinationand over-etching of the underlying silicon-containing layers. Diluteinorganic acid/amine complexes and inorganic acids contemplated hereininclude pyridine/HF complex, pyridine/HCl complex, pyridine/HBr complex,triethylamine/HF complex, triethylamine/HCl complex, fluorosilicic acid,hydrofluoric acid, tetrafluoroboric acid, and triethylamine/formic acidcomplex, and combinations thereof with peroxides, concentrated HCl,ammonium hydroxide, and mixtures thereof. These compositions may beaqueous-based, solvent-based, or combinations thereof. For example,solvents contemplated herein for the depassivating solution include, butare not limited to, water, DMSO, methanol, ethyl acetate, any of theother aforementioned solvents, and combinations thereof. It is to beunderstood that following depassivation, the depassivating compositionwill include some amount of SAM compounds.

Yet another aspect of the invention relates to the improvedmicroelectronic devices made according to the methods of the inventionand to products containing such microelectronic devices.

A still further aspect of the invention relates to methods ofmanufacturing an article comprising a microelectronic device, saidmethod comprising contacting the microelectronic device with aSAM-containing composition for sufficient time to at least partiallyremove bulk and hardened photoresist material from the microelectronicdevice having said photoresist material thereon, and incorporating saidmicroelectronic device into said article, wherein the SAM-containingcomposition includes at least one solvent, at least one catalyst, atleast one SAM component, and optionally at least one surfactant.Alternatively, the SAM-containing composition may further include adense fluid.

The features and advantages of the invention are more fully shown by theillustrative example discussed below.

EXAMPLE 1

Atomic Force Microscopy (AFM) and surface energy measurements wereperformed before and after contact of a sample device surface with theSAM-containing compositions of the invention to determine the extent ofremoval of hardened photoresist as well as monolayer formation on thesurface of said device. The sample device surfaces included wafersconsisting of (from top to bottom) an ion-implanted photoresist layer(2×10¹⁵ As ions cm⁻²; 10 keV implant energy), a bulk photoresist layer,a silicon-containing gate oxide layer, and a silicon substrate. Thesamples were processed for varying times and at varying temperaturesusing varying SAM functionalities, and the contact angles measured. Theresults are tabulated in Tables 1-3 hereinbelow. TABLE 1 Processing as afunction of time using a SAM-containing composition including 1 mmolCl₃SiMe and 2 mmol Et₃N in 10 mL of toluene, and a contactingtemperature of 70° C. Time Contact Angle (°) 0 (control) 35 ± 3 10 min77 ± 2 30 min 79 ± 1 1 hour 80 ± 1 15 hours 95 ± 4

TABLE 2 Processing as a function of temperature using a SAM-containingcomposition including 1 mmol Cl₃SiMe and 2 mmol Et₃N in 10 mL oftoluene, and a contacting time of 30 min. Temperature/° C. Contact Angle(°) control 35 ± 3 50° C. 75 ± 2 60° C. 79 ± 2 70° C. 79 ± 1

TABLE 3 Processing as a function of SAM functionalities using aSAM-containing composition including 1 mmol of the listed SAM and 2 mmolEt₃N in 10 mL of toluene, at a contacting temperature of 70° C. for acontacting time of 30 min. SAM Contact Angle (°) Cl₃SiMe 79 ± 1Cl₂Si(Me)₂ 86 ± 1 ClSi(Me)₃ 97 ± 1 Cl₃SiH 87 ± 4

Passivation of the underlying silicon-containing layer is evidenced byan increase in the contact angle following application of theSAM-containing composition with the device surface. It can be seen inTable 1 that a process time of less than 10 minutes is needed totransform the hydroxyl-terminated hydrophilic device surface, having acontact angle of 35 degrees, to a methyl-terminated hydrophobic surface,having a contact angle of 77 degrees.

The corresponding AFM images illustrated in FIGS. 1A-1D, at contactingtimes equal to 10 min, 30 min, 1 hour and 15 hours, respectively,clearly show that as time increased (while maintaining all other processparameters constant), small islands form on the silicon-containingsurface due to polymerization (or cross-linking) of themulti-substituted chlorosilane. As process time is increased, theislands gradually coalesce, or agglomerate, and at 15 hours showevidence of bulk polymerization on the surface.

The preliminary temperature studies were performed to determine the mosteffective temperature for surface passivation and cleaning efficiency.With regards to cleaning efficiency, four different microelectronicdevice layers were considered: bulk blanketed photoresist; the 30-45 nmion-implanted crust on the bulk blanketed photoresist; bulk patternedphotoresist; and the ion-implanted crust on the bulk patternedphotoresist. Comparing the results reported in Table 2 (the contactangles) with the percent removal efficiency illustrated in FIG. 2, itcan be seen that temperatures greater than 60° C. provide the greatestamount of passivation as well as almost 100% removal of photoresist.Accordingly, all subsequent experiments as a function of time and SAMfunctionality were performed at 70° C.

The evidence of cross-linking is better shown in FIGS. 3A-3C, whichillustrate the variation of cross-linking as a function of SAMfunctionality, specifically the number of chloride leaving groups, attemperature of 70° C. and time of 30 min. It can be seen that withClSiMe₃ (FIG. 3A), the ability of the SAM to cross-link does not exist,and a smooth monolayer (rms=0.415 nm; control rms=0.131 nm) is formed onthe surface. However, with Cl₂SiMe₂ (FIG. 3B) and Cl₃SiMe (FIG. 3C),cross-linking occurs as evidenced by the island formation describedhereinabove, which as a result, leads to rougher film surfaces(rms=0.465 and 1.573 nm for the di- and tri-chlorosilanes,respectively). The formation of islands is indicative of the necessityfor more aggressive depassivation techniques (e.g., more concentratedcompositions, greater contact time, etc.).

EXAMPLE 2

FIGS. 4A-4C show the optical (FIG. 4A) and scanning electron microscopic(SEM) images of sample device surfaces including a layer of denselypatterned, highly doped (2×10¹⁵ As ions cm²; 10 keV implant energy)photoresist consisting of a region of parallel lines. The 30 nm thickhardened crust can be clearly seen in the 90 degree angle view image(FIG. 4C). The cleaning efficiency of the crust as a function ofchloride substitution on the SAM component is illustrated in FIG. 5A(ClSiMe₃), FIG. 5B (Cl₂SiMe₂), and FIG. 5C (Cl₃SiMe). The opticalmicroscope images in FIGS. 5A-5C illustrate that as the number ofchloride leaving groups on the SAM component increases, the amount ofhardened photoresist removed also increases. In fact, greater than 90%removal of the four different microelectronic device layers isachievable using the Cl₃SiMe-containing composition (see FIG. 6). It isthought that the increase in crust removal is the result of an increasein HCl generated when the SAM-containing composition is applied to thedevice surface.

An additional experiment was performed whereby a non-halide containingSAM-containing composition was contacted with the sample device surfaceincluding densely patterned, highly doped photoresist and underlyingsilicon-containing layer(s). No hardened photoresist was removed, eventhough the sample was passivated as evidenced by the contact angle of63°. Therefore, our results show that some amount of leaving group,e.g., chloride, is necessary for hardened photoresist removal.

EXAMPLE 3

A further aspect of the invention includes the removal of thepassivating layer from the surface of the microelectronic device, or“depassivation.” FIG. 7A is an optical microscope image of a denselypatterned device surface having a contact angle of 36° and an rms=0.15nm. FIG. 7B is an optical image of the device surface of FIG. 7Afollowing application at 70° C. for 30 min of a SAM-containingcomposition including Cl₃SiMe. The contact angle of the passivatedsurface was determined to be 79° (with a rms=1.10 nm), evidencingpassivation of the silicon-containing surface. It can be seen that atleast 90% of the hardened photoresist was removed. FIG. 7C is an opticalimage of the device surface of FIG. 7B following depassivation at 50° C.for 2 min using NEt₃:HF (1:3 mole ratio) in DMSO composition. Thecontact angle of the depassivated surface was determined to be 35° (witha rms=0.25 nm). Once the contact angle of the surface matches that ofthe surface prior to contact with the SAM-containing composition, thedepassivation process is essentially complete.

It is noted that the depassivation process should be optimized in orderto eliminate fluorination and/or over-etching of the underlyingsilicon-containing layer(s). For example, depassivation may be performedin 30 second intervals for SAM removal from thermal oxide-containingdevice structures and 20 second intervals for SAM removal fromTEOS-based device structures.

FIGS. 8A-8E provide another illustration of the passivation and cleaningresults, as well as depassivation following removal of the hardenedphotoresist. FIG. 8A is a SEM of a device surface including a denselypatterned, highly doped (2×10¹⁵ As ions cm⁻²; 10 keV implant energy)photoresist layer prior to processing. FIG. 8B is a SEM of the denselypatterned surface of FIG. 8A following application at 70° C. for 30 minof a SAM-containing composition including Cl₃SiMe, illustrating thesuccessful and efficient removal (and passivation) of the hardenedphotoresist. FIGS. 8C and 8D are SEMs of the device surface of FIG. 8Bfollowing depassivation at 50° C. for 2 min using NEt₃:HF (1:3 moleratio) in DMSO composition. The SEM image in FIGS. 8C and 8D do not showany evidence of substantial over-etching of the underlyingsilicon-containing layers during the depassivation process (compare withthe over-etched sample in FIG. 8E).

The improved SAM-containing compositions taught herein effectivelyremove bulk and hardened photoresist in a one-step or multi-stepprocess, without the need for a plasma etch step and withoutsubstantially over-etching the underlying silicon-containing layer(s).

Accordingly, while the invention has been described herein in referenceto specific aspects, features and illustrative embodiments of theinvention, it will be appreciated that the utility of the invention isnot thus limited, but rather extends to and encompasses numerous otheraspects, features and embodiments. Accordingly, the claims hereafter setforth are intended to be correspondingly broadly construed, as includingall such aspects, features and embodiments, within their spirit andscope.

1. (canceled)
 2. A method of removing bulk and hardened photoresistmaterial from a microelectronic device having said photoresist materialthereon, said method comprising contacting the microelectronic devicewith a SAM-containing composition for sufficient time and undersufficient contacting conditions to at least partially remove saidphotoresist material from the microelectronic device, wherein theSAM-containing composition includes at least one solvent, at least onecatalyst, at least one SAM component, and optionally at least onesurfactant.
 3. The method of claim 2, wherein said contacting is carriedout at conditions selected from the group consisting of: time of fromabout 1 minute to about 60 minutes; temperature in a range of from about30° C. to about 80° C., and combinations thereof.
 4. (canceled)
 5. Themethod of claim 2, wherein the solvent comprises at least one solventselected from the group consisting of toluene, decane, octane, dodecane,pentane, hexane, tetrahydrofuran (THF), carbon dioxide, methanol,ethanol, isopropanol, N-methylpyrrolidinone, N-octylpyrrolidinone,N-phenylpyrrolidinone, dimethylsulfoxide (DMSO), sulfolane, ethyllactate, ethyl acetate, toluene, acetone, butyl carbitol,monoethanolamine, butyrol lactone, diglycol amine, alkyl ammoniumfluoride, γ-butyrolactone, butylene carbonate, ethylene carbonate,propylene carbonate, and mixtures thereof; wherein the catalystcomprises an amine selected from the group consisting of trimethylamine,triethylamine, butylamine, pyridine, and combinations thereof; andwherein the SAM component comprises a silane selected from the groupconsisting of: (RO)₃SiX, (RO)₂SiX₂, (RO)SiX₃, (R)₃SiX, (R)₂SiX₂, and(R)SiX₃, where X=F, Cl, Br and I, and R=methyl, ethyl, propyl, butyl,octyl, decyl, and dodecyl; fluorinated derivatives thereof; andcombinations thereof.
 6. The method of claim 2, wherein the mole ratioof SAM(s) relative to catalyst(s) in a liquid SAM-containing compositionis in a range from about 1:10 to about 5:1 and the mole ratio of SAM(s)relative to solvent(s) is in a range from about 1:200 to about 1:50. 7.The method of claim 2, wherein the microelectronic device comprises anarticle selected from the group consisting of semiconductor substrates,flat panel displays, and microelectromechanical systems (MEMS).
 8. Themethod of claim 2, wherein the bulk and hardened photoresist materialscomprise dopant ions selected from the group consisting of arsenic ions,boron ions, phosphorous ions, indium ions, and antimony ions.
 9. Themethod of claim 2, wherein the contacting comprises a process selectedfrom the group consisting of: spraying the SAM-containing composition ona surface of the microelectronic device; dipping the microelectronicdevice in a sufficient volume of SAM-containing composition; contactinga surface of the microelectronic device with another material that issaturated with the SAM-containing composition; contacting themicroelectronic device with a circulating SAM-containing composition;contacting the microelectronic device with a continuous flow of theSAM-containing composition; and contacting the microelectronic devicesurface with a static volume of the SAM-containing composition for acontinued period of time.
 10. The method of claim 2, further comprisingrinsing the microelectronic device following contact with theSAM-containing composition.
 11. The method of claim 2, wherein the atleast one SAM component and the at least one catalyst are present inamounts effective to simultaneously passivate a silicon-containing layeron said microelectronic device and remove bulk and hardened photoresistmaterial from the microelectronic device having said material thereon.12. The method of claim 11, wherein the silicon-containing layercomprises a silicon-containing compound selected from the groupconsisting of silicon; silicon dioxide; TEOS; silicon nitride;silicon-containing organic polymers; silicon-containing hybridorganic/inorganic materials; organosilicate glass (OSG); fluorinatedsilicate glass (FSG); carbon-doped oxide (CDO) glass; and combinationsthereof.
 13. The method of claim 11, wherein the underlyingsilicon-containing layer has a contact angle in a range from about 60degrees to about 120 degrees following formation of the SAM-passivatinglayer.
 14. The method of claim 2, further comprising removing aSAM-passivating layer from the microelectronic device with adepassivating composition following at least partial removal of saidphotoresist material from the microelectronic device.
 15. The method ofclaim 14, wherein the depassivating composition comprises compoundsselected from the group consisting of pyridine/HF complexes,pyridine/HCl complexes, pyridine/HBr complexes, triethylamine/HFcomplexes, fluorosilicic acid, hydrofluoric acid, tetrafluoroboric acid,triethylamine/HCl complexes, triethylamine/formic acid complexes,peroxide derivatives thereof, concentrated HCl, ammonium hydroxide, andcombinations thereof.
 16. The method of claim 2, wherein the solventcomprises dense carbon dioxide.
 17. The method of claim 16, wherein saidcontacting comprises conditions selected from the group consisting of:pressure in a range of from about 1500 to about 4500 psi; time in arange of from about 5 to about 30 minutes; temperature in a range offrom about 40° C. to about 75° C.; and combinations thereof. 18.(canceled)
 19. (canceled)
 20. (canceled)
 21. A method of removing a selfassembled monolayer (SAM) passivating layer from a microelectronicdevice with a depassivating composition, wherein the depassivatingcomposition comprises compounds selected from the group consisting ofpyridine/HF complexes, pyridine/HCl complexes, pyridine/HBr complexes,triethylamine/HF complexes, fluorosilicic acid, hydrofluoric acid,tetrafluoroboric acid, triethylamine/HCl complexes, triethylamine/formicacid complexes, peroxide derivatives thereof, concentrated HCl, ammoniumhydroxide, and combinations thereof.
 22. A self assembled monolayer(SAM)-containing composition, comprising at least one solvent, at leastone catalyst, at least one SAM component, and optionally at least onesurfactant, wherein said SAM-containing composition is suitable forremoving bulk and hardened photoresist material from a microelectronicdevice having said photoresist material thereon.
 23. The SAM-containingcomposition of claim 22, wherein the mole ratio of SAM(s) relative tocatalyst(s) in a liquid SAM-containing composition is in a range fromabout 1:10 to about 5:1, and the mole ratio of SAM(s) relative tosolvent(s) is in a range from about 1:200 to about 1:50.
 24. TheSAM-containing composition of claim 22, wherein the solvent comprises atleast one non-polar solvent selected from the group consisting oftoluene, decane, dodecane, octane, pentane, hexane, tetrahydrofuran(THF), carbon dioxide, and mixtures thereof.
 25. The SAM-containingcomposition of claim 24, further comprising an additional solventselected from the group consisting of methanol, ethanol, isopropanol,N-methylpyrrolidinone, N-octylpyrrolidinone, N-phenylpyrrolidinone,dimethylsulfoxide (DMSO), sulfolane, ethyl lactate, ethyl acetate,toluene, acetone, butyl carbitol, monoethanolamine, butyrol lactone,diglycol amine, alkyl ammonium fluoride, γ-butyrolactone, butylenecarbonate, ethylene carbonate, propylene carbonate, and mixturesthereof.
 26. The SAM-containing composition of claim 22, wherein thesolvent comprises toluene.
 27. The SAM-containing composition of claim22, wherein the solvent comprises dense carbon dioxide.
 28. TheSAM-containing composition of claim 22, wherein the SAM componentcomprises a silane selected from the group consisting of: (RO)₃SiX,(RO)₂SiX₂, (RO)SiX₃, (R)₃SiX, (R)₂SiX₂, and (R)SiX₃, where X=F, Cl, Brand I, and R=methyl, ethyl, propyl, butyl, octyl, decyl, and dodecyl;fluorinated derivatives thereof; and combinations thereof.
 29. TheSAM-containing composition of claim 22, wherein the SAM componentcomprises an alkylchlorosilane selected from the group consisting ofCl₃SiMe, Cl₂SiMe₂, and ClSiMe₃.
 30. The SAM-containing composition ofclaim 22, wherein the catalyst comprises an amine selected from thegroup consisting of trimethylamine, triethylamine, butylamine, pyridine,and combinations thereof.
 31. The SAM-containing composition of claim22, comprising at least one surfactant.
 32. The SAM-containingcomposition of claim 22, wherein the surfactant comprises a surfactantspecies selected from the group consisting of fluoroalkyl surfactants,polyethylene glycols, polypropylene glycols, polyethylene glycol ethers,polypropylene glycol ethers, carboxylic acid salts,dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid salts,polyacrylate polymers, dinonylphenyl polyoxyethylene, silicone polymers,modified silicone polymers, acetylenic diols, modified acetylenic diols,alkylammonium salts, modified alkylammonium salts, and combinationsthereof.
 33. The SAM-containing composition of claim 22, wherein thecomposition comprises toluene, Cl₃SiMe and triethylamine.
 34. TheSAM-containing composition of claim 22, wherein the microelectronicdevice comprises an article selected from the group consisting ofsemiconductor substrates, flat panel displays, andmicroelectromechanical systems (MEMS).
 35. The SAM-containingcomposition of claim 22, wherein the bulk and hardened photoresistmaterials comprise dopant ions selected from the group consisting ofarsenic ions, boron ions, phosphorous ions, indium ions and antimonyions.
 36. The SAM-containing composition of claim 22, wherein the atleast one SAM component and the at least one catalyst are present inamounts effective to simultaneously passivate a silicon-containing layeron said microelectronic device and remove bulk and hardened photoresistmaterial from the microelectronic device having said material thereon.37. The SAM-containing composition of claim 36, wherein thesilicon-containing layer comprises a silicon-containing compoundselected from the group consisting of silicon; silicon dioxide; TEOS;silicon nitride; silicon-containing organic polymers; silicon-containinghybrid organic/inorganic materials; organosilicate glass (OSG);fluorinated silicate glass (FSG); carbon-doped oxide (CDO) glass; andcombinations thereof.
 38. The SAM-containing composition of claim 27,wherein the carbon dioxide is supercritical.
 39. The SAM-containingcomposition of claim 22, further comprising photoresist residuematerial, wherein the photoresist comprises bulk photoresist, hardenedphotoresist, or combinations thereof.
 40. The SAM-containing compositionof claim 39, wherein the photoresist comprises an ion selected from thegroup consisting of boron ions, arsenic ions, phosphorus ions, indiumions, antimony ions, and combinations thereof.
 41. A kit comprising, inone or more containers, SAM-containing composition reagents, wherein theSAM-containing composition comprises at least one solvent, at least onecatalyst, at least one SAM component, and optionally at least onesurfactant, and wherein the kit is adapted to form a SAM-containingcomposition suitable for removing bulk and hardened photoresist materialfrom a microelectronic device having said photoresist material thereon.42. A method of manufacturing a microelectronic device, said methodcomprising contacting the microelectronic device with the SAM-containingcomposition of claim 22 for sufficient time to at least partially removebulk and hardened photoresist material from the microelectronic devicehaving said material thereon.